CN103890022B - 异戊二烯醇、单烯属不饱和一元羧酸和磺酸的共聚物及其生产方法和用途 - Google Patents
异戊二烯醇、单烯属不饱和一元羧酸和磺酸的共聚物及其生产方法和用途 Download PDFInfo
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- CN103890022B CN103890022B CN201280049579.XA CN201280049579A CN103890022B CN 103890022 B CN103890022 B CN 103890022B CN 201280049579 A CN201280049579 A CN 201280049579A CN 103890022 B CN103890022 B CN 103890022B
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229920001577 copolymer Polymers 0.000 title claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 14
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 17
- -1 sulfhydryl compound Chemical class 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- SAJLIOLJORWJIO-UHFFFAOYSA-N hydroxymethanesulfinic acid;sodium Chemical compound [Na].OCS(O)=O SAJLIOLJORWJIO-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 12
- 239000001506 calcium phosphate Substances 0.000 claims description 10
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 10
- 235000011010 calcium phosphates Nutrition 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000003009 phosphonic acids Chemical class 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 5
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 claims description 3
- AIIITCMZOKMJIM-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)(C)NC(=O)C=C AIIITCMZOKMJIM-UHFFFAOYSA-N 0.000 claims description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 3
- VSSGDAWBDKMCMI-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CS(O)(=O)=O VSSGDAWBDKMCMI-UHFFFAOYSA-N 0.000 claims description 3
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- BZRJNHACGRRFSN-UHFFFAOYSA-N OC(C(=O)O)=S=O.[Na] Chemical compound OC(C(=O)O)=S=O.[Na] BZRJNHACGRRFSN-UHFFFAOYSA-N 0.000 claims description 3
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- DPZFPPWWSNNMPI-UHFFFAOYSA-N [S]C=C Chemical compound [S]C=C DPZFPPWWSNNMPI-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 166
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000003112 inhibitor Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 229920001897 terpolymer Polymers 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000033228 biological regulation Effects 0.000 description 10
- 239000011790 ferrous sulphate Substances 0.000 description 10
- 235000003891 ferrous sulphate Nutrition 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 150000004688 heptahydrates Chemical class 0.000 description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 10
- 229920002125 Sokalan® Polymers 0.000 description 9
- 239000004584 polyacrylic acid Substances 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- 230000001629 suppression Effects 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 239000011976 maleic acid Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229940120146 EDTMP Drugs 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- SVZNRBAZGGBJOW-UHFFFAOYSA-N (2-methylprop-2-enoylamino)methanesulfonic acid Chemical compound CC(=C)C(=O)NCS(O)(=O)=O SVZNRBAZGGBJOW-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KKSNTCYLMGYFFB-UHFFFAOYSA-N (prop-2-enoylamino)methanesulfonic acid Chemical compound OS(=O)(=O)CNC(=O)C=C KKSNTCYLMGYFFB-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 1
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- QLYHVLWJJRLFJQ-UHFFFAOYSA-N CCC(CCCCC)(CC)P(O)(O)=O.OCC Chemical group CCC(CCCCC)(CC)P(O)(O)=O.OCC QLYHVLWJJRLFJQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
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- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
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- 239000002738 chelating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Abstract
本发明涉及一种具有如下单体的共聚物:(a)5‑40重量%异戊二烯醇,(b)5‑93重量%至少一种单烯属不饱和C3‑C8单羧酸或其酸酐或盐,(c)2‑90重量%一种或多种含磺酸基团的单体。
Description
本发明涉及异戊二烯醇、单烯属不饱和一元羧酸和磺酸的共聚物,其生产方法及其在含水体系中作为沉积物抑制剂的用途。
水中绝大部分物质的溶解度是受限的。特别是在工业水处理中,防止含水体系中矿物质沉积物是一个重要任务。无机盐,如碳酸钙、氢氧化镁、硫酸钙和硫酸钡以及磷酸钙或膦酸钙在水中溶解度低。如果这些溶解的组分在含水体系中富集(变稠),则超过产品的溶解度,结果是这些物质沉淀出来并造成沉积。此外,物质的溶解度取决于温度和pH。许多物质,如碳酸钙或硫酸钙尤其显示反向溶解度,即它们的溶解度随着温度增加而降低。这使得高的工艺温度经常导致不希望的沉淀和沉积物在冷却和锅炉进料水体系中在热交换表面或管中形成。
无机物质和盐在含水体系中的沉淀和沉积只可能费力的除去。各种机械和化学清洁是需要花费资金和时间的并且不可避免的导致生产失败。
不仅在冷却和锅炉进料水体系中希望防止碳酸钙沉积物、硫酸钙沉积物和其他盐沉积物的形成。而且在通过蒸馏和通过薄膜方法如反渗透或电渗析的海水脱盐中,也努力防止这些固体沉积物的形成。
对多功能沉积物抑制剂存在特别的关注,所述多功能沉积物抑制剂对碳酸钙、硫酸钙、磷酸钙和膦酸钙沉积物具有良好的抑制性能。这对于常规沉积物抑制剂如聚丙烯酸来说是有问题的。该均聚物经常对碳酸钙或磷酸钙而言是良好的沉积物抑制剂,但是尤其对于磷酸钙和膦酸钙几乎不具有抑制活性。
将借助自由基聚合制备的低分子量聚丙烯酸及其盐用作工业水处理和海水脱盐中的沉积物抑制剂是已知的(这是因为它们的分散剂性能和抑制晶体生长性能)。对于良好的活性,这些聚合物的平均分子量(Mw)应该<50 000g/mol。Mw<10 000g/mol的聚丙烯酸经常描述为特别有效。这些
聚合物的一个缺点在于随着温度增加它们对硬度的敏感增加,即聚合物作为聚丙烯酸的钙盐或镁盐沉淀的风险增加。此外,聚丙烯酸对于磷酸钙或膦酸钙的沉积仅具有非常低的抑制活性。
腐蚀保护在工业水工艺中是不可缺少的。在常规的腐蚀抑制剂中,磷酸盐和膦酸盐显示了突出的重要性。然而,随着将磷酸盐或膦酸盐用作腐蚀抑制剂,来自磷酸钙或膦酸钙沉积物的风险也随之增加。这些沉积物是特别有问题的,因为它们又需要花大力气才能除去。
除了,纯的聚丙烯酸外,作为沉积物抑制剂还描述了许多共聚物、三元共聚物和四元共聚物。例如描述了,不饱和羧酸如丙烯酸、含磺酸盐单体如2-丙烯酰胺基-2-甲基丙烷磺酸盐、苯乙烯磺酸盐或甲基丙烯酸磺乙酯以及任选非离子单体的一般共聚物。非离子单体通常为丙烯酰胺、丙烯酰胺衍生物如N-烷基丙烯酰胺、甲基丙烯酰胺、丙烯酸烷基酯、丙烯酸羟基烷基酯、甲基丙烯酸烷基酯或乙酸乙烯酯。
US4,711,725描述了(1)(甲基)丙烯酸(2)丙烯酰胺基烷基-或–芳基磺酸酯,尤其是2-丙烯酰胺基-2-甲基丙烷磺酸酯(AMPS)和(3)乙烯基酯,如丙烯酸乙酯和甲基丙烯酸羟基乙酯,或丙烯酰胺如叔丁基丙烯酰胺的三元共聚物作为含水体系的沉积物抑制剂。
US4,952,327描述了(1)(甲基)丙烯酸或马来酸、(2)丙烯酰胺基链烷磺酸,尤其是AMPS和(3)苯乙烯磺酸的三元共聚物作为含水体系的沉积物抑制剂。
JP59102496描述了0.5-50重量%不饱和醇如异戊二烯醇与50-99.5重量%烯属单或二羧酸,如丙烯酸或马来酸以及任选0-40重量%第三单体的共聚物的制备,所述第三单体尤其包括苯乙烯磺酸盐、丙烯腈或乙酸乙烯酯。所得聚合物被描述为工业水处理中的结壳抑制剂。在95℃使用过氧化氢和过硫酸钠的混合物作为单体引发剂。所得聚合物的分子量为3200-4000g/mol。
EP-A337694涉及50-99.9重量%马来酸和50-0.1重量%水溶性不饱和共聚单体的马来酸共聚物的制备及其在水处理中的用途,所述共聚物的数均分子量Mn为300-5000g/mol且多分散性<2.5。特别提及了作为清洁 配制剂中的防垢剂和助洗剂。所述共聚单体尤其为单烯属不饱和单羧酸,如丙烯酸和甲基丙烯酸,不饱和二羧酸,如富马酸和衣康酸,不饱和醇,如异戊二烯醇,(甲基)烯丙基醚,和单烯属不饱和含磺酸基团的化合物,如乙烯基磺酸和2-丙烯酰胺基-2-甲基丙烷磺酸。共聚物通过用H2O2作为引发剂在0.5-500ppm含铁、铜或钒离子的金属催化剂存在下的水性聚合制备。没有使用链转移剂。在聚合过程中,释放二氧化碳,其中二氧化碳的量与H2O2的量成比例。在实施例中,制备了马来酸-异戊二烯共聚物,该共聚物的分子量为1090-4780g/mol,其中聚合在单体水溶液的沸点下进行。
EP-A396303涉及75-100重量%马来酸和0-25重量%其他水溶性单体的马来酸聚合物的制备,其中通过用12-150g H2O2/mol单体组分、0.3-500ppm铁、钒或铜的金属盐,以及碱性物质,如碱金属氢氧化物或碱金属碳酸盐(用于中和至多45重量%具有酸基的单体)进行水性聚合。所述共聚单体尤其为不饱和单羧酸,如丙烯酸和甲基丙烯酸,不饱和二羧酸,如富马酸和衣康酸,不饱和醇,如异戊二烯醇,(甲基)烯丙基醚,和不饱和含磺酸基团的化合物,如乙烯基磺酸和2-丙烯酰胺基-2-甲基丙烷磺酸。未使用链转移剂。据说聚合温度为85-160℃。在实施例中,制备了数均分子量为2400-4100g/mol的80重量%马来酸和20重量%异戊二烯醇的共聚物。聚合在单体混合物的沸点下进行。描述了共聚物作为助洗剂和防垢剂的用途。
现有技术方法的缺点为可如此得到的含异戊二烯醇共聚物的较窄分子量范围以及高聚合温度,在所述高聚合温度下,烯属醇,如异戊二烯醇经受化学降解(参见F.Lynen,Liebigs Ann.Chem.1960,360,58-70)。与之相关的是,对应于现有技术的含异戊二烯醇聚合物的活性降低。
本发明的目的是,提供多功能的沉积抑制聚合物,其具有尽可能宽的对抗钙和镁盐的沉淀物和沉积物的活性,并且对于抑制碳酸钙、硫酸钙、磷酸钙和膦酸钙在含水体系中沉淀和沉积尤其有效。此外,本发明的目的是提供一种制备所述共聚物的方法。
该目的通过如下组分的共聚物实现:
(a)5-40重量%异戊二烯醇,
(b)5-93重量%至少一种单烯属不饱和C3-C8单羧酸,其酸酐或盐,
(c)2-90重量%一种或多种含磺酸基团的单体。
可用作单体(b)的合适的单烯属不饱和C3-C8单羧酸例如为丙烯酸、甲基丙烯酸、乙基丙烯酸、乙烯基乙酸、烯丙基乙酸和巴豆酸及其水溶性盐。如果羧酸不饱和C3-C8单羧酸可形成酸酐,这些酸酐也适合作为单体(b),如马来酸酐。
优选单烯属不饱和C3-C8单羧酸(b)为丙烯酸、甲基丙烯酸、乙基丙烯酸、乙烯基乙酸、烯丙基乙酸和巴豆酸,特别优选丙烯酸和甲基丙烯酸。
含磺酸基团的单体(c)优选为式(Ia)和(Ib)的那些:
H2C=CH-X-SO3H (Ia),
H2C=C(CH3)-X-SO3H (Ib),
其中X为任选存在的间隔基团,其可选自其中n为0-4的-(CH2)n-、-C6H4-、-CH2-O-C6H4-、-C(O)-NH-C(CH3)2-、-C(O)-NH-CH(CH2CH3)-、-C(O)NH-CH(CH3)CH2-、-C(O)NH-C(CH3)2CH2-、-C(O)NH-CH2CH(OH)CH2-、-C(O)NH-CH2-、-C(O)NH-CH2CH2-和-C(O)NH-CH2CH2CH2-。
此时,特别优选含磺酸基团的单体为1-丙烯酰胺基-1-丙烷磺酸(X=-C(O)NH-CH(CH2CH3)于式IIa中)、2-丙烯酰胺基-2-丙烷磺酸(X=-C(O)NH-CH(CH3)CH2-于式IIa中)、2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS,X=-C(O)NH-C(CH3)2CH2-于式IIa中)、2-甲基丙烯酰胺基-2-甲基丙烷磺酸(X=-C(O)NH-C(CH3)2CH2-于式IIb中)、3-甲基丙烯酰胺基-2-羟基丙烷磺酸(X=-C(O)NH-CH2CH(OH)CH2于式IIb中)、烯丙基磺酸(X=CH2于式IIa中)、甲基烯丙基磺酸(X=CH2于式IIb中)、烯丙基氧基苯磺酸(X=-CH2-O-C6H4-于式IIa中)、甲基烯丙基氧基苯磺酸(X=-CH2-O-C6H4-于式IIb中)、2-羟基-3-(2-丙烯氧基)丙烷磺酸、2-甲基-2-丙烯-1-磺酸(X=CH2于式IIb中)、乙烯基磺酸(X不存在于式IIa中)、丙烯酸3-磺丙酯(X=-C(O)O-CH2CH2CH2-于式IIa中)、甲基丙烯酸2-磺乙酯(X=-C(O)O-CH2CH2-于式IIb中)、甲基丙烯酸3-磺丙酯(X=-C(O)O-CH2CH2CH2-于式IIb中)、磺基甲基丙烯酰胺(X=-C(O)NH-于式 IIb中)、磺基甲基甲基丙烯酰胺(X=-C(O)NH-CH2-于式IIb中)以及所述酸的盐。合适的盐通常是水溶性盐,优选所述酸的钠、钾和铵盐。
特别优选1-丙烯酰胺基丙烷磺酸、2-丙烯酰胺基-2-丙烷磺酸、2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)、2-甲基丙烯酰胺基-2-甲基丙烷磺酸、3-甲基丙烯酰胺基-2-羟基丙烷磺酸、甲基丙烯酸2-磺乙酯、磺酸、乙烯基磺酸、烯丙基磺酸(ALS)和甲基烯丙基磺酸以及所述酸的盐。
非常特别优选含磺酸基团的单体为2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)和烯丙基磺酸及其水溶性盐,特别是其钠盐、钾盐和铵盐。特别优选AMPS。
共聚物的重均分子量通常为2000-20000g/mol,优选2500-15000g/mol,特别优选3000-13000g/mol。
分子量借助凝胶渗透色谱法与聚丙烯酸标样相比而测定。
共聚物的多分散性指数通常为Mw/Mn≤2.5,优选≤2.0。
本发明共聚物通常包含5-35重量%异戊二烯醇(a),30-80重量%单烯属不饱和C3-C8羧酸(b)和5-50重量%含磺酸基团的单体(c)。特别优选它们包含5-30重量%异戊二烯醇(a),50-80重量%单烯属不饱和C3-C8羧酸(b)和10-30重量%含磺酸基团的单体(c)。本发明共聚物的显著之处尤其在于,它们通过特别温和的聚合方法得到,其中没有发生副反应,如异戊二烯醇异构化为戊二烯醇(prenol)或二甲基乙烯基甲醇,形成3-甲基-1,3-丁二醇或异戊二烯或马来酸脱羧。
制备含异戊二烯醇的共聚物的已知方法基于在约100℃的升高温度下的自由基聚合。已知的是,异戊二烯醇特别是在酸性条件和高温下快速化学降解(F.Lynen,Liebigs Ann.Chem.1960,360,58-70)。与之相反,本发明方法使得在10-80℃的温度下的显著温和条件下的聚合反应变得可行。从而有效防止了异戊二烯醇的降解。优选聚合在10-70℃,特别优选在10-60℃下进行。
本发明方法通常以进料流程序半连续进行。所用溶剂通常为水。
根据优选实施方案,聚合在单体含量为25-50重量%的水溶液中进行。此时,自由基聚合在酸性条件下,通常在pH0.5-6.5下进行。优选以如下 方式进行,所有单体(a)、(b)和(c)以进料加入,其中单烯属不饱和C3-C8单羧酸(b),如丙烯酸也可部分中和。异戊二烯醇(a),单烯属不饱和C3-C8单羧酸(b)如丙烯酸,和含磺酸基团的单体(c),如2-丙烯酰胺基-2-甲基丙烷磺酸也可首先全部或部分装入。例如,单体(c)可位于接收器中且单体(a)和(b)可作为进料加入。作为单体(c)的(甲基)烯丙基磺酸酯优选首先装入。
在另一实施方案中,聚合在单体含量为25-50重量%的水/甲醇混合物中进行。在特定实施方案中,将甲醇中的异戊二烯醇作为进料加入。在聚合结束之后,可在减压下除去甲醇,其中聚合物水溶液优选以30-60重量%的固含量得到。
还原剂通常以单独的进料加入。这降低了过氧化物引发剂的活化阈值,从而使得共聚可在低温下进行。
氧化还原引发剂通常包含过氧化物和还原剂。
合适的过氧化物例如为过氧化氢,过二硫酸钠,过二硫酸钾或过二硫酸铵,氢过氧化叔丁基,过氧化二苯甲酰或氢过氧化枯基。在优选实施方案中,引发剂包含过氧化氢。过氧化氢通常以水溶液使用,例如过氧化氢含量为30重量%的水溶液。
过氧化氢优选位于接收器中,但是也可作为进料加入。
合适的还原剂例如为亚铁(II)盐,羟基甲烷亚磺酸钠(例如可以Rongalit 或Brüggolit SFS)得到),钠-2-羟基-2-亚磺酰基乙酸(例如可以Brüggolit FF06得到),抗坏血酸,碱金属亚硫酸盐和碱金属焦亚硫酸盐,次磷酸钠和硫脲。在优选实施方案中,引发剂包含羟基甲烷亚磺酸钠或钠-2-羟基-2-亚磺酰基乙酸作为还原剂。
在另一优选实施方案中,引发剂除了过氧化物和还原剂之外还包含铁盐。
在特别优选的实施方案中,氧化还原化学引发剂包含过氧化氢、铁盐以及还原剂。
合适的链转移剂为无机硫化合物,如亚硫酸氢盐、焦亚硫酸盐、连二亚硫酸盐,有机硫化物,亚砜和巯基化合物,如巯基乙醇、巯基乙酸,以及无机磷化合物,如次磷酸及其盐,如次磷酸钠。
在优选实施方案中,链转移剂包含巯基化合物,尤其是巯基乙醇。
链转移剂通常至少部分以进料加入。子量的链转移剂也可位于接收器中。
本发明还涉及所述共聚物在抑制含水体系中的钙盐沉淀和沉积中的用途,尤其是用于抑制碳酸钙、硫酸钙、磷酸钙或膦酸钙的沉淀和沉积。本发明共聚物的显著之处在于它们抑制两种或更多种所述钙盐的沉淀。
使用含异戊二烯醇的共聚物的含水体系特别为冷却水体系和锅炉进料水体系,以及海水脱盐装置。
本发明聚合物通常以0.1mg/l-100mg/l的量加入含水体系中。最佳剂量取决于各应用要求和各方法的操作条件。例如,在海水的热脱盐中,优选以0.5mg/l-10mg/l的浓度使用聚合物。在工业冷却循环或锅炉进料水体系中,使用至多100mg/l的聚合物浓度。经常进行水分析以确定形成沉积物的盐比例以及最佳剂量。
也可将配制剂加入含水体系中,所述配制剂除了本发明共聚物之外,根据要求还可尤其包含膦酸盐、聚磷酸盐、锌盐、钼酸盐,有机腐蚀抑制剂,如苯并***、甲苯基***、苯并咪唑或乙炔基甲醇烷氧基化物,生物杀伤剂,络合剂和/或表面活性剂。膦酸盐的实例为1-羟基乙烷-1,1-二膦酸(HEDP)、2-膦酰丁烷-1,2,4-三甲酸(PBTC)、氨基三亚甲基膦酸(ATMP)、二亚乙基三胺五(亚甲基膦酸)(DTPMP)和乙二胺四(亚甲基膦酸)(EDTMP),它们可以以酸形式或以其钠盐形式使用。
本发明通过下面的实施例更详细说明。
实施例
中分子量借助GPC测定。
设备:Waters Alliance2690,具有UV-检测器(Waters2487)和RI检测器(Waters2410)
柱:Shodex OHpak SB804HQ和802.5HQ
(PHM胶,8×300mm,pH4.0-7.5)
洗脱液:0.05M含水甲酸铵/甲醇混合物=80:20(体积份)
流速:0.5ml/min
温度:50℃
注射:50-100μl
检测:RI和UV
聚合物的分子量相对于来自Varian Inc.的聚丙烯酸标样测定。聚丙烯酸标样的分子量分布曲线通过光散射测定。聚丙烯酸标样的质量为115000、47500、28000、16000、7500、4500、4100、2925和1250g/mol。合成实施例
实施例1
IP/AS/AMPS(10/70/20)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入125g去离子水、0.5g2-巯基乙醇和0.02g硫酸亚铁(II)七水合物,,并将其带至20℃的聚合启动温度并维持(接收器)。在单独的进料容器中,提供81g浓度为90重量%的丙烯酸(溶液A)。将10g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将45g浓度为50重量%的AMPS水溶液与4g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后在接收器混合物中加入14g过氧化氢(30重量%水溶液)。向搅拌的接收器中同时加入溶液A、溶液B、溶液C和溶液D。
溶液A以80g/h的计量速率经60分钟加入
溶液B平行地以10g/h的计量速率经60分钟加入。
溶液C平行地以49g/h的计量速率经60分钟加入。
溶液D平行地以20g/h的计量速率经70分钟加入。
然后使用浓度为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为37%,共聚物的中分子量为Mw4900g/mol。
实施例2
IP/AS/AMPS(10/70/20)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装 入125g去离子水、0.5g2-巯基乙醇和0.02g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持(接收器)。在单独的进料容器中,提供81g90重量%丙烯酸(溶液A)。将10g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将45g50重量%AMPS水溶液与2g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g中的第三溶液(溶液D)。然后将14g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A、溶液B、溶液C和溶液D。
此时溶液A以80g/h的计量速率经60分钟加入。
溶液B平行地以10g/h的计量速率经60分钟加入。
溶液C平行地以47g/h的计量速率经60分钟加入。
溶液D平行地以20g/h的计量速率经70分钟加入。
然后使用浓度为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为36重量%。共聚物的中分子量为Mw10000g/mol。
实施例3
IP/AS/AMPS(15/60/25)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入125g去离子水,0.5g2-巯基乙醇和0.02g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,提供81g浓度为90重量%的丙烯酸(溶液A)。将18g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将66g浓度为50重量%的AMPS水溶液与4g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将14g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A以80g/h的计量速率经60分钟加入。
溶液B平行地以18g/h的计量速率经60分钟加入。
溶液C平行地以70g/h的计量速率经60分钟加入。
溶液D平行地以20g/h的计量速率经70分钟加入。
然后使用浓度为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为39重量%。共聚物的中分子量为Mw6500g/mol。
实施例4
IP/AS/AMPS(20/60/20)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入125g去离子水,0.5g2-巯基乙醇和0.02g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,提供81g浓度为90重量%的丙烯酸(溶液A)。将24g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将53g浓度为50重量%的AMPS水溶液与2g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将14g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A此时以80g/h的计量速率经60分钟加入。
溶液B平行地以24g/h的计量速率经60分钟加入。
溶液C平行地以55g/h的计量速率经60分钟加入。
溶液D平行地以20g/h的计量速率经70分钟加入。
然后使用浓度为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为39%。共聚物的中分子量为Mw11000g/mol。
实施例5
IP/AS/ALS(10/70/20)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入140g去离子水,20g烯丙基磺酸钠,0.5g2-巯基乙醇和0.02g硫酸亚铁 (II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,提供81g浓度为90重量%的丙烯酸(溶液A)。将10g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将15g水与4g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将14g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A以80g/h的计量速率经60分钟加入。
溶液B平行地以10g/h的计量速率经60分钟加入。
溶液C平行地以19g/h的计量速率经60分钟加入。
溶液D平行地以20g/h的计量速率经60分钟加入。
然后使用浓度为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为38重量%。共聚物的中分子量为Mw5400g/mol。
实施例6
IP/AS/ALS(10/75/15)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入27g去离子水,14g烯丙基磺酸钠,40g甲醇,0.5g2-巯基乙醇和0.01g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,提供81g浓度为90重量%的丙烯酸(溶液A)。在另一单独的进料容器中,将9g异戊二烯醇与32g甲醇(溶液B)混合。在另一单独的进料容器中,将10g水与3.5g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将6g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A此时以120g/h的计量速率经40分钟加入。
溶液B平行地以61g/h的计量速率经40分钟加入。
溶液C平行地以21g/h的计量速率经40分钟加入。
溶液D平行地以10g/h的计量速率经60分钟加入。
然后在减压下除去甲醇。然后使用浓度为50重量%的氢氧化钠溶液将剩余聚合物水溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为49%。共聚物的中分子量为Mw4000g/mol。
实施例7
IP/AS/ALS(15/65/20)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入115g去离子水,21g烯丙基磺酸钠,0.5g2-巯基乙醇和0.01g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,将81g浓度为90重量%的丙烯酸与64g水(溶液A)混合。将16.5g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将10g水与3.5g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将6g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A此时以145g/h的计量速率经60分钟加入。
溶液B平行地以16.5g/h的计量速率经60分钟加入。
溶液C平行地以13.5g/h的计量速率经60分钟加入。
溶液D平行地以12g/h的计量速率经60分钟加入。
然后在减压下除去甲醇。然后使用浓度约为50重量%的氢氧化钠溶液将剩余聚合物水溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为38重量%。共聚物的中分子量为Mw6200g/mol。
实施例8
IP/AS/ALS(20/60/20)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入140g去离子水,31g烯丙基磺酸钠,0.5g2-巯基乙醇和0.02g硫酸亚铁 (II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,提供81g浓度为90重量%的丙烯酸(溶液A)。将24g异戊二烯醇装入(溶液B)另一单独的进料容器中。在另一单独的进料容器中,将15g水与3g2-巯基乙醇(溶液C)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将14g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A以80g/h的计量速率经60分钟加入。
溶液B平行地以24g/h的计量速率经60分钟加入。
溶液C平行地以18g/h的计量速率经60分钟加入。
溶液D平行地以20g/h的计量速率经70分钟加入。
然后使用浓度约为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为41%。共聚物的中分子量为Mw8100g/mol。
对比例A
聚丙烯酸A
在反应器中,将304.0g去离子水与1.84g浓度为50重量%的亚磷酸水溶液一起装入并在氮气气氛下加热至98℃的内部温度。在该温度下,分开且平行地同时搅拌加入461.0g蒸馏的丙烯酸,132.0g浓度为7重量%的过二硫酸钠溶液和196.0g浓度为40重量%的亚硫酸氢钠水溶液。丙烯酸经4小时加入,过二硫酸钠经4.25小时加入且亚硫酸氢钠经3.75小时加入。在丙烯酸进料结束之后,在98℃的内部温度下经1小时加入496.0g浓度为50重量%的氢氧化钠水溶液,并且在98℃下再继续聚合1小时。然后,将聚合物溶液冷却至室温。得到略微粘胶的透明聚合物溶液,pH为6.9且固含量为43.5%。重均分子量(Mw)为4450g/mol。
对比例B
AS/AMPS(80/20)–共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装 入100g去离子水,0.5g2-巯基乙醇和0.01g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持。在单独的进料容器中,提供88g浓度为90重量%的丙烯酸(溶液A)。在另一单独的进料容器中,将40g浓度为50重量%的AMPS水溶液与3.5g2-巯基乙醇(溶液B)混合。与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液C)。然后将6g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B和溶液C。
溶液A以88g/h的计量速率经60分钟加入。
溶液B平行地以44g/h的计量速率经60分钟加入。
溶液C平行地以10g/h的计量速率经60分钟加入。
然后使用浓度约为50重量%的氢氧化钠溶液将所得聚合物溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为39重量%。共聚物的中分子量为Mw6500g/mol。
对比例C
AS/AMPS/tBAM(70:20:10)-三元共聚物
在配有搅拌器、温度计、pH电极和多个进料器具的玻璃反应器中,装入70g去离子水,0.25g2-巯基乙醇和0.02g硫酸亚铁(II)七水合物,并将其带至20℃的聚合启动温度并维持(接收器)。在单独的进料容器中,用62g50%的氢氧化钠溶液(溶液A)中和80g浓度为90重量%的丙烯酸。在另一单独的进料容器中,将41g浓度为50重量%的AMPS水溶液与4g2-巯基乙醇(溶液B)混合。在另一进料溶液中,将12g叔丁基丙烯酰胺与45g甲醇(溶液C)混合。
与之平行地,制备5g羟基甲烷亚磺酸钠(Brüggolit SFS,来自Brüggemann GmbH)在45g水中的第三溶液(溶液D)。然后将6g过氧化氢(30重量%水溶液)加入接收器混合物中。向搅拌的接收器中同时加入溶液A,溶液B,溶液C和溶液D。
溶液A此时以80g/h的计量速率经60分钟加入。
溶液B平行地以45g/h的计量速率经60分钟加入。
溶液C平行地以47g/h的计量速率经60分钟加入。
溶液D平行地以15g/h的计量速率经70分钟加入。
然后,在减压下除去甲醇。然后使用浓度为50重量%的氢氧化钠溶液将剩余聚合物水溶液调节至pH2.6。
所得共聚物以无色溶液产生,其固含量为40重量%。共聚物的中分子量为Mw5800g/mol。
碳酸钙抑制测试
将NaHCO3,Mg2SO4,CaCl2和聚合物的溶液在70℃下在水浴中震摇2h。在通过0.45μm Milex过滤器过滤仍然温热的溶液之后,通过使用电感耦合等离子的发射光谱(ICP-OES)测定滤液的Ca含量以及根据式I通过CaCO3抑制前/后的对比以%确定Ca含量。
条件
式I:
CaCO3-抑制(%)=24小时后mg(Ca2+)–24小时后mg(Ca2+)空白值/mg(Ca2+)零值–24小时后mg(Ca2+)空白值×100
硫酸钙抑制测试
将NaCl,Na2SO4,CaCl2和聚合物的溶液在70℃下在水浴中震摇24h。在通过0.45μm Milex过滤器过滤仍然温热的溶液之后,通过使用电感耦合等离子的发射光谱(ICP-OES)测定滤液的Ca含量以及根据下文式II通过 CaSO4抑制前/后的对比以%确定Ca含量。
条件:
式II:
CaSO4-抑制(%)=24h后mg(Ca2+)–24h后空白值mg(Ca2+)/mg(Ca2+)零值-24h后空白值mg(Ca2+)×100
磷酸钙抑制测试
将H3PO4,CaCl2,NaHCO3,MgSO4和聚合物的溶液在70℃下在水浴中震摇24h。在通过0.45μm Milex过滤器过滤仍然温热的溶液之后,通过使用电感耦合等离子的发射光谱(ICP-OES)测定滤液的磷酸盐含量以及根据下文式III通过Ca3(PO4)2抑制前/后的对比以%确定磷酸盐含量。
条件:
式III:
Ca3(PO4)2-抑制(%)=24h后mg(PO4 3-)–24h后空白值mg(PO4 3-)/mg(PO4 3-)零值-24h后空白值mg(PO4 3-)×100
测试结果总结在下表中。
表
缩写:
IP=异戊二烯醇
AS=丙烯酸
ALS=烯丙基磺酸钠盐
AMPS=2-丙烯酰胺基-2-甲基丙烷磺酸
tBAM=叔丁基丙烯酰胺
Claims (17)
1.一种具有如下单体的共聚物:
(a)5-40重量%异戊二烯醇,
(b)5-93重量%至少一种单烯属不饱和C3-C8单羧酸,其酸酐或盐,
(c)2-90重量%一种或多种单烯属不饱和含磺酸基团的单体。
2.根据权利要求1的共聚物,其中所述单烯属不饱和C3-C8单羧酸(b)选自丙烯酸、甲基丙烯酸、乙基丙烯酸、乙烯基乙酸、烯丙基乙酸和巴豆酸。
3.根据权利要求2的共聚物,其中所述单烯属不饱和C3-C8单羧酸(b)为丙烯酸或甲基丙烯酸。
4.根据权利要求1的共聚物,其中所述单烯属不饱和含磺酸基团的单体(c)选自1-丙烯酰胺基丙烷磺酸、2-丙烯酰胺基-2-丙烷磺酸、2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)、2-甲基丙烯酰胺基-2-甲基丙烷磺酸、3-甲基丙烯酰胺基-2-羟基丙烷磺酸、甲基丙烯酸2-磺乙酯、苯乙烯磺酸、乙烯基磺酸、烯丙基磺酸(ALS)和甲基烯丙基磺酸。
5.根据权利要求4的共聚物,其中所述单烯属不饱和含磺酸基团的单体(c)为2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)或烯丙基磺酸。
6.根据权利要求1的共聚物,其中其重均分子量为2000-20 000g/mol。
7.根据权利要求6的共聚物,其中存在5-30重量%异戊二烯醇(a),50-80重量%单烯属不饱和C3-C8羧酸(b)和10-30重量%单烯属不饱和含磺酸基团的单体(c)。
8.一种制备具有如下单体的共聚物的方法:
(a)5-40重量%异戊二烯醇,
(b)5-93重量%至少一种单烯属不饱和C3-C8单羧酸,其酸酐或盐,
(c)2-90重量%一种或多种单烯属不饱和含磺酸基团的单体,
其中所述单体(a)、(b)和(c)在氧化还原化学引发剂和链转移剂存在下,在10-80℃的温度下聚合。
9.根据权利要求8的方法,其中所述氧化还原化学引发剂包含过氧化物和还原剂。
10.根据权利要求9的方法,其中所述氧化还原化学引发剂额外包含铁盐。
11.根据权利要求9的方法,其中所述氧化还原化学引发剂包含过氧化氢作为过氧化物。
12.根据权利要求9的方法,其中所述氧化还原化学引发剂包含羟基甲烷亚磺酸钠或钠-2-羟基-2-亚磺酰基乙酸作为还原剂。
13.根据权利要求8的方法,其中所述链转移剂包含巯基化合物。
14.根据权利要求1-7中任一项的共聚物在含水体系中作为沉积物抑制剂的用途。
15.根据权利要求1-7中任一项的共聚物在含水体系中抑制钙盐或镁盐沉淀和沉积中的用途。
16.根据权利要求15的用途,其用于抑制碳酸钙、硫酸钙、磷酸钙或膦酸钙的沉淀和沉积。
17.根据权利要求15的用途,其用于海水脱盐装置、微咸水脱盐装置、冷却水体系和锅炉进料水体系。
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CN105647678B (zh) * | 2016-01-14 | 2018-05-15 | 广州立白企业集团有限公司 | 提升洗涤组合物对蛋白污垢去除能力的方法及洗涤剂组合物 |
CN114671982A (zh) * | 2022-02-24 | 2022-06-28 | 浙江鑫月新材料科技有限公司 | 一种减缩型聚羧酸减水剂及其制备方法 |
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- 2012-07-23 CN CN201280049579.XA patent/CN103890022B/zh active Active
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EP0206814A2 (en) * | 1985-06-26 | 1986-12-30 | Rohm And Haas Company | Water-soluble polymers and their use in the stabilization of aqueous systems |
US5135677A (en) * | 1988-04-11 | 1992-08-04 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
US5064563A (en) * | 1989-04-28 | 1991-11-12 | Nippon Shokubai Co., Ltd. | Process for producing and use of maleic acid (co-) polymer salt improved in biodegradability |
CN1203962A (zh) * | 1997-05-09 | 1999-01-06 | 罗姆和哈斯公司 | 水垢抑制剂 |
EP1182217A2 (en) * | 2000-08-22 | 2002-02-27 | Nippon Shokubai Co., Ltd. | Novel water-soluble copolymer and its production process and use |
Also Published As
Publication number | Publication date |
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AU2012292468B2 (en) | 2015-11-05 |
AU2012292468A1 (en) | 2014-02-27 |
MX353846B (es) | 2018-01-31 |
MX2014001453A (es) | 2014-02-27 |
JP6120847B2 (ja) | 2017-04-26 |
CA2844514C (en) | 2019-07-16 |
ES2568912T3 (es) | 2016-05-05 |
EP2742075B1 (de) | 2016-03-02 |
TN2014000053A1 (en) | 2015-07-01 |
JP2014528977A (ja) | 2014-10-30 |
RU2014108708A (ru) | 2015-09-20 |
KR101879183B1 (ko) | 2018-08-17 |
MA35339B1 (fr) | 2014-08-01 |
BR112014002935A2 (pt) | 2017-04-04 |
IL230885A (en) | 2017-02-28 |
CA2844514A1 (en) | 2013-02-14 |
KR20140045554A (ko) | 2014-04-16 |
BR112014002935B1 (pt) | 2020-10-13 |
EP2742075A1 (de) | 2014-06-18 |
CN103890022A (zh) | 2014-06-25 |
RU2632991C2 (ru) | 2017-10-12 |
WO2013020799A1 (de) | 2013-02-14 |
IL230885A0 (en) | 2014-03-31 |
CL2014000335A1 (es) | 2014-08-01 |
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